Cyclic polymeric chloromethylphenoxy phosphonitriles

ABSTRACT

WHEREIN M IS AN INTEGER OF FROM 1 TO 3 INCLUSIVE AND WITH THE PROVISO THAT AT LEAST ONE OF THE R and Ra   WHEREIN X IS AN INTEGER OF FROM 3 TO 7 AND WHEREIN THE R and Ra substituent of each polymeric unit of the above formula areindependently selected from the group consisting of phenyl or   Cyclic polymeric chloromethylphenoxy phosphonitriles having the formula:

United States Patent [72] Inventors 3,291,865 12/1966 Koberetal.

Ehrenl'ried H. Kober l-lamden;

Henry F. Lederle, North Haven; Gerhard F. Ottmann, l-lamden, all oi Conn.

Appi. No. 777,927

Filed June 3, 1968 Patented Dec. 14, 1971 Assignee Olin Corporation New Haven, Conn. Original application Nov. 15, 1965, Ser. No. 507,660, now Patent No. 3,450,799. Divided and this application June 3, 1968, Ser. No. 777,927

CYCLIC POLYMERIC CHLOROMETHYLPHENOXY PHOSPHONITRILES 2 Claims, No Drawings I [1.8. Ci 260/927 N, 252/78, 260/2, 260/77.5, 260/968, 260/973 int. Cl ..C07d 105/02, C07f 9/24, C09j 3/28 Field of Search 260/927 N, 968

References Cited UNITED STATES PATENTS OTHER REFERENCES Organic Reactions, Vol. I, John Wiley & Sons, inc. (New York), I954, pages 68 and 69.

Yokoyama. Chemical Abstracts, Vol. 56 1962) page 502.

ABSTRACT: Cyclic polymeric chloromethyiphcnoxy 'phosphonitn'les having the formula.

wherein x is an integer of from 3 to 7 and wherein the R and R, substituent of each polymeric unit of the above formula areindependentiy selected from the group consisting of phenyl (CHgCDm wherein m is an integer of from 1 to 3 inclusive and with the proviso that at least one of the R and R subslituents is (CHaCD CYCLIC POLYMERIC CHLOROMETHYLPHENOXY PHOSPHONITRILES This application is a division of copending application Ser. No. 507,660, filed Nov. 15, 1965, by Ehrenfried H. Kober,

Henry F. Lederle and Gerhard F. Ottmann, now US. Pat. No. 5

cyclic polymeric cyclic polymeric to a method for wherein x is an integer of from 3 to 7 wherein the R and R substituents of each polymeric unit of the formula:

are independently selected from the group consisting of phenyl or (onion...

wherein m is an integer of from 1 to 3 inclusive and with the proviso that at least one of the R and R substituents is (CHzCDm The formula of the polymeric hydroxymethylphenoxy phosphonitriles of this invention is shown below:

are independently selected from the group consisting of phenyl or (CHiCDm and R wherein m is an integer of from 1 to 3 inclusive and with the proviso that at least one of the R, and& substituents is onion...

Preparation of the polymeric chloromethylphenoxy phosphonitriles of this invention is accomplished in good yield by reacting a chloromethyl ether of the formula:

ClCH -OR,, wherein R, is alkyl of from one to six carbon atoms, with a cyclic polymeric phenoxy phosphonitrile of the formula:

wherein x is an integer of from 3 to 7. The reaction is conducted in the presence of an inert solvent which can be, for example. carbon disulfide' or carbon tetrachloride and in the presence of stannic chloride which serves as catalyst. The chloromethylated product can be recovered from the two phase reaction mixture by any convenient method, such as by extraction with a lower dialkyl ether (for example, diethyl ether) followed by evaporation of the solvent. lf chloromethylation of each of the phenoxy groups of the starting phosphonitrile is desired, not less that the stoichiometric requirement of the chloromethyl alkyl ether is employed. if partial chloromethylation is the objective, the quantity of the ether is reduced to the appropriate molar stoichiometric necessity.

Cyclic polymeric phenoxy phosphonitriles of the formula where .r is an integer of from 3 to 7 can be prepared by heating a phosphonitrile chloride and phenol in the presence of sodium hydroxide as described by F itzsimmons and Shaw, 1. Chem. Soc., 1964, p. 1735.

The cyclic polymeric chloromethylphenoxy phosphonitriles of this invention, that is cyclic polymeric compounds of the formulawherein x is an integer of from 3 to 7 and wherein the R and R substituents of each polymeric unit of the formula:

Lap 11 are independently selected from the group consisting of phenyl or omcnm wherein m is an integer of from 1 to 3 inclusive and with the proviso that at least one of the R and R,, substituents is can be hydrolyzed by heating at a temperature of from about th oro ethyl ethyl et er g., 26 le). mer- 60 to about 150 C. and in the presence of alcoholic alkali ic (p xylp osphonitrile (42-6 g., 0.184 mole) and 240 metal hydroxide such as odiu potassium h d id to ml. of carbon disulfide. Stirring was started and then 30.0 g. of yield hydrox'y derivatives of the formula: Stannic chloride 13.5 ml.) was added via the dropping funnel 5 during a period of about 2 hours, the temperature being maintained at 26-31 C. Stirring at room temperature was con- ORb"' tinued for another 4 hours. After standing for 3 days, the product, composed of two L layers, was poured over ice water and extracted with ether. 0 The ether extracts were then dried over magnesium sulfate containing a small amount of potassium carbonate. After tiltration of the drying agent, the solvent was stripped first at 60 C. bottoms temperature at atmospheric pressure, and then to wherein .r is an integer of from 3 to 7 and wherein the R and 65 C. at water aspirator pressure to give 49.4 g. of product.

R substituents of each polymeric unit of the formula: t 1 5 The product contained 9.77 percent chlorine corresponding approximately to an average of 2.2 chloromethyl groups per molecule of the phosphonitrile.- s EXAMPLE m i 7" g Trimeric bis(phenoxy)phosphonitrile was reacted with chloromethyl methyl ether under the same conditions as set forth in example I] except that stirring at room temperature are independently selected from the group consisting of phenwas carried Out for 90 hours after addition of -I W yl and 25 completed. After isolation of the reaction product as CH OH described in example ll, the resulting chloromethylated product was found by analysis to contain approximately 12.5 chloromethyl groups per molecule of the phosphonitriles.

1 3o EXAMPLE [V wherein "I is an integer Of 1 t0 3 inclusive and the chlo omethylated trimeric bi5(phenoxy)pho5ph nin-i|e proviso that at least one of the R and R substituents is (8.2 g.) prepared in example l, containing 6.87 percent chlorine, was dissolved in 80 ml. of ethanol containing 10 g. of L H2 :Dm dissolved potassium hydroxide. The mixture was stirred and 3s refluxed for 6.5 hours.

The cooled product was poured into an excess of water, ex-

' tracted with ether, the ether extracts washed with water and The novel cyclic polymeric hydroxymethylphenoxy dried over magnesium sulfate. After filtration of the drying phosphonitriles can be reacted with a diisocyanate in the 40 agent, the solvent was stripped first to 55 C. bottoms at atpresence of a suitable fluorocarbon blowing agent to yield mospheric pressure, then to 70C.- at water aspirator pressure. fire-resistant polyurethane products or the polymeric hydrox- A yield of 5 g. of the hydroxymethylphenoxy phosphonitrile ymethylphenoxy phosphonitriles can be reacted with an alproduct was obtained. The chlorine content of this product kyleneoxide, such as ethylene, oxide, propylene oxide or a was less that 0.06 percent, indicating that the hydrolysis of the hydroxyalkylene oxide, such as glycidol, to yield water-soluble 5 chlorine to hydroxyl groups was essentially quantitative. oxyalkylated products suitable for use in hydraulic fluids or in What is Claimed is: the preparation of polyurethane foams and coatings. l. A cyclic polymeric phosphonitrile compound of the for- Examples which illustrate various embodiments of this inmula: v vention and which are to be considered not limitative follow:

. Y /OR 1 EXAMPLE I A 250 ml. three neck flask was charged with chloromethyl i n -ix methyl ether (25 g., 0.3l3 moles), trimeric bis(phenox- I wphosphommle Q0306 moles) and [20 of wherein x is an integer of from 3 to 7 and wherein the R and hen disulfide. The mixture was stirred and cooled to 0 C. Rasubstimems ofeach polymeric f h f la;

Stannic chloride (15 g., 0.0576 moles), was then added through a dropping funnel during a period of 50 minutes. A

slight exotherm was noted. After the addition had been finished, the resulting two-layer reaction mixture was stirred L J for another hour and then permitted to warm to room tem- 5 Perature. are independently selected from the group consisting of phen- After standing for 2 days, the mixture waspoured over ice yl and and the organic layer was taken up in ether, washed, and dried over magnesium sulfate. After filtration and after stripping first to 60 C. bottoms temperature at atmospheric pressure and then to l00 C. at water aspirator pressure, a yield of 23.l

g. of the chloromethylated product was obtained. A chlorine wherein m i an i t ger amsiii'fa 3 inclusive, and with the analysis indicated that this material contained 6.87 percent proviso that at least one f the R substituems is chlorine corresponding approximately to an average of 1.75 (CHCDm chloromethyl groups per mole of the phosphonitrile.

EXAMPLE ll wmd m A 500 ml. three neck flask, fitted with a thermometer, con- The compound ofclaim 1 wherein X is denser, magnetic stirrer and dropping funnel, was charged, n: n: 4 t 

2. The compound of claim 1 wherein x is
 3. 